Alpha,omega-dihalo-geminal-dinitro compositions



This invention relates to new compositions 'of matter and methods for producing the same and is related in particular to dihalo geminal dinitro aliphatic compositions having the general formula: A

wherein A is a lower alkylene radical and X is a chlorine or bromine radical.

This application is a continuation-in-part of my pending application Serial No. 439,458, filed June 25, 1954, now abandoned, which was a continuation-in-part of application Serial No. 203,559, filed December 29, 1950, subsequently abandoned.

The dihalogen compounds of this invention are used as starting materials in the preparation of nitro-substituted diesters as disclosed in my copending application Serial No. 652,308, filed concurrently with the present application. The diesters thus obtained undergo ester interchange to form nitro diols and the resulting nitro diols readily react with diisocyanate compositions such as methylene diisocyanate to form nitro polyurethanes, as disclosed in assignees copending application Serial No. 328,515, filed December 29, 1952, now abandoned. The nitro polyurethanes thus obtained are useful as a primary propulsion source in rocket-propelled vehicles, and can also be used as a propellant for artillery missiles. When used as the primary propulsion source for rocket vehicles, they can be conveniently ignited by a conventional igniter, as for example the igniter disclosed in assignees copending United States patent application Serial No. 306,030, filed August 23, 1952. The propellant is preferably cast in tubular form and restricted in the conventional manner with a relatively inert resin, such as a non-nitrated polyurethane foam or a polyester resin, and placed inside a chamber having one end open and leading into a conventional venturi rocket nozzle. Upon ignition, large quantities of gases are produced and exhausted through the nozzle creating propulsive force.

The dihalogen compounds of this invention are conveniently prepared by the reaction of bromine or chlotime upon the corresponding di-silver dialkanoates in accordance with the general reaction scheme set forth below:

wherein A is a lower alkylene radical and X is bromine or chlorine.

The reaction temperature is non-critical in the practice of this invention, the only eflect of temperature variation being a corresponding increase or decrease in reaction rate which in turn results in a corresponding increase or decrease in reaction time.

To more clearly illustrate my invention, the following example is provided. It should be understood that 3,000,969 Pa e ted Sept. '19, 1951 this example is presented purely for illustrative purposes and should not be construed as limiting the invention to the particular conditions set forth therein.

EXAMPLE Preparation of 3, 3-dinizro lfi-pentanedibromigig A'three neckedflask, fitted with amercury sealed stir rer, thermometer, and condenser, having a calcium chloride drying tube and a dropping funnel connected there to, is charged with 132 ml. (412 gins; 2.57 moles) of. dry bromine and 60 0 ml. of carbon tetrachloride.

A dispersion of 550 grams -(1.10 moles) of the dried silver salt of 4.4-dinitro-1,7-heptanedioic acid in 4000 ml. of carbon tetrachloride is slowly added to the bromine so-.

it is neutral, with dilute acid until the solution is just acid and washed with water until neutral. The carbon tetrachloride is evaporated from the mixture and'the residue is distilled at a temperature varying between and 122 C. and under a pressure of 1-2 mm. This yields, 3,3-dinitro-l,5-pentane dibromide which has a refractiye index of n 1.5348. When this material is redistilled the refractive index is n 1.5354.

This compound, having the formula C H N O Br has a calculated composition of: Percent C, 18.77; percent 1H, 2.52; percent N, 8.76; percent Br, 49.95, by weight. The results obtained by ultimate analysis are: Percent C, 19.81; percent H, 2.64; percent N, 8.17; percent 'Br, 49.37, by weight.

Homologues of these compounds are prepared simply by reacting the corresponding silver salt in the manner described in Example I.

wherein A is a lower alkylene radical and X is a halogen radical selected from the group consisting of bromine and chlorine.

2. As compositions of matter, the dibromo-nitroalkanes having the formula:

No: a Bl'AGHr-%-CH5A-B1 wherein A is a lower alkylene radical.

3. As a composition of matter, 3,3-dinitro-l,5-pentanedibromide, having the structural formula:

The diacids are prepared 4: Th t d 9i prepmhg a dihalo nitroallsane whieh comprises reacting a halogen selected from the group consisting of chlorine and bromine with a silver nitrollsan a-te having he formula:

n I [I Ag-O-C-A--CHa-l3-CHa-A-COAg wherein A is a lower alkylene radical.

:5. Th method f preparing a dibiomomitroalkan whieh comp i e re cti g bromin wi h a si ver ni r alkanoate having the? f rmula:

wherein A is a lower alkylene raglieal.

6. The method of preparing 3,3-dinitro-l,5-pemane-di- 4 bromide whieh comprises reacting bromine and di-silver 4,4-dinitro-1,7-heptanedioate.

References Cited in the file of this patent UNITED STATE PATENTS H 2,289,546 Leeher et 1111. H July 14, '1942 2,3 9,89 T n all "9 Feb- 2, 194.3 2,357,912 McBee et a1- nmme-me D c. 28, 19 3 OTHER REFERENCES Royals: Advaneed Organic Chemistry," pages 5658 (1956), Prentice Hall, Inc., NJ.

Sehrnidt et al.: Ber. 59B, 1876-88 (1926).

Macbeth .et al.: Iour. Chem. Soc. 1932, 534943.

Downing et al.: Jour. Ch m; Soc. 1934, 167142.

Hass et al.: Chem. Rev." 32, 421, 425, 427 (June 1943).

Hurd et al.: J.A.C.S. 55, 699-702 (1933). 

1. AS COMPOSITIONS OF MATTER, THE DIHALO-NITROALKANES HAVING THE FORMULA:
 4. THE METHOD OF PREPARING A DIHALO-NITROALKANE WHICH COMPRISES REACTING A HALOGEN SELECTED FROM THE GROUP CONSISTING OF CHLORINE AND BROMINE WITH A SILVER NITROALKANOATE HAVING THE FORMULA: 